Upload
hoanglien
View
226
Download
0
Embed Size (px)
Citation preview
DC CVD
Development of DC pulse plasma CVD system with minimum
chamber volume and control of substrate temperature
1185071
28 2 15
1 p1
1.1
2 (Diamond-Like Carbon: DLC) p2
2.1 DLC
2.2 DLC
2.3 DLC
2.3.1 FCVA(Filtered Cathodic Vaccum Arc)
2.3.2 CVD(Chemical Vapor Deposition)
2.4 DLC
3 CVD p9
3.1 CVD
3.2 CVD
3.3 DC
3.4
3.5
3.6
3.7
4 DC DLC p21
4.1 CO DLC
4.1.1
4.1.2 DC
4.1.3
4.2
5 p28
1
1
1.1
Diamond-Like Carbon: DLC
CD
DLC
2
CVD DLC
DLC
tetrahedral amorphous
carbon: ta-C80 GPa 3 g/cm3
3.52 g/cm3 ta-C
Filtered Cathodic Vaccum Arc: FCVA
CVD
DLC DLC CVD
DLCC2H2 C6H6 C H
50 atm%
Konishi [1] CVD
DLC 6 % DLC 2
CVD
(CO) DLC
[2]CO DLC 15 GPa
4 atm% 20 atm%
CVD CVD
DLC
CVD
CVD
CO CVD ta-C
2
2 (Diamond-Like Carbon)
DLC CVD ta-
C
2.1 DLC
Diamond-Like Carbon: DLC
sp3
sp2
DLC
sp3 sp2
Amorphous-CarbonDLC
DLC 2.1 [3]DLC
2.1 [3]
2.1 DLC 2.2DLC
DLC
DLC
DLC
DLC
(g/cm3) 2.26 1.52.5 3.52
(HV) 100 10005000 800010000
(cm) 410-3 1071014 10131016
2.15 22.4 2.42
(eV) - 12 5.5
(GPa) - 100500 1150
(W/cmK) 0.42.1 0.2 620
() 600 300400 600
3
2.1 DLC [3]
2.2 DLC [3]
2.2 DLC
2.2 2.3 DLC[4] 2.2 sp3
DLC sp3
()ta-C(Tetrahedral amorphous Carbon) sp3 ()ta-
C:H(Hydrogenated Tetrahedral amorphous Carbon)sp3 sp2
()a-C(Amorphous Carbon) sp3 sp2 ()a-
C:H(Hydrogenated Amorphous Carbon) sp2
()GLC(Graphite Like Carbon) sp2()PLC(Polymer
Like Carbon) DLCPLC(1.4 g/cm3)
DLC
PET
()
4
0.59 GPa[4] 70 %
()
2.2 DLC [4]
2.3 DLC [4]
DLC
sp3sp2sp3
sp2
2.3 DLC
DLC
0
10
20
30
40
50
60
70
80
90
100
0.1 1 10 100
sp3
[
H [atm]
sp
3
[]
H
[atm]
ta-C 50sp390 H5
ta-C:H 50sp3100 5H50
a-C H5
a-C:H 5H50
GLC 0sp320 (0H5)
PLC - (50H70) sp3205H
- (70H)
20sp350
5
Physical Vapor DepositionPVDChemical Vapor DepositionCVD
PVD
CVD
PVD DLC
CVD
DLCElectron cyclotron Resonance: ECR
Radio Frequency: RF CVD CVD
sp3 ta-C
Filtered Cathodic Vaccum Arc: FCVA
CVD
2.3.1 FCVAFiltered Cathodic Vaccum Arc
m
DLC
FCVA
m
[5] 2.3
2.3.2 CVDChemical Vapor Deposition
Chemical Vapor Deposition: CVD
CVD CVD CVD CVD [6] 2.4
RF 13.56MHzMW 2.45GHz
CVD150300
[7-8]DLC
CH4 C2H2
6
CVD DLC
CVD DLC
a-C:H
sp3
5atm%ta-C 2590 GPa
3.52.6g/cm3[4]sp3 550atm% ta-C:H
935GPa 2.62.0g/cm3
CVD a-C:H 1025GPa 2.0
1.4g/cm3
2.3 FCVA[5]
Vaccum arc supply
v
vv
+
-
++
+
+
+
++
+ +
--
--
-
-
-
+
+ +
+
+
+
+
+
+
+
+ +
+
+
+
+ Su
bst
rate
Striker
Filter field
Focusing
magnetic field
Optical viewport
Substrate bias
7
2.4 CVD[6]
2.4 DLC
DLCRobertson
2.5
sp3 -
100 V sp38[9]
DLC
-100V sp3[10]
FCVA(Arc Ion Plating: AIP)100
eV sp3 9 DLC
CVD
CVD 100 eV
200300 eV [11]
sp3
700 1000DLC 500
FCVA
200 CVD
Konishi[1] CVDDLC
26% 23%250 DLC
2
(13.56 MHz)
+ +--
8
2.5 [8]
ta-C FCVA
ta-C
CVD a-C:H
CVD ta-C DLC
CVD ta-CDLC
sp3
DLC CO RF
CVD DLC CO DLC 15 GPa
4 atm% 20 atm%CO
DLC
RF CVD
CVD
CVD CO CVD ta-
C
relaxationpenetration
direct
9
3 CVD
CVD
CVD DC
3.1 CVD
3.1 CVD
3.2 CVD
3.2
3.2 CVD
3.1 CVD
DC
RF
10
3.2 CVD
3.2 CVD
CVD 3.3
1.6 L RF CVD[2] 1/17
CVD
4
120 mm 3.4
CVD (90 mm)CVD
2 mm
3.5
DC
RF
11
3.3 CVD
3.4 CVD
80 mm
160 mm
CVD90 mm)
12
3.5
Ar 10 Pa
V-130-5
3.6 400400
15 250 W 400
60 W 1 400
2 100
3.6
3.3 DC
DC
[12-13]DC
100 200
100
200
300
0
100
200
300
400
500
0
Po
wer
(W
)
Ele
ctro
de
tem
per
atu
re (
)
Time (min)
Ar 10 Pa
13
[14] 3.7 P 2
d V R
DC
Vb
Vd RVb=Vd-RId
Vd R 3.8 Id-Vd Id-Vd
3.7 DC
3.8 DC (Id-Vd)
Vd R
dP
Vb
Id
Vd
Id
Vd-RId
Id
14
3.9DCAr
(MFC) Ar 100 sccm
(TMP)(RP)
2.666 kPaMKS
4 (SUS304)
10 k15
k100 k200 k1 M 1 k
+1 kDC TMK1.0-50
PA500-0.1A(KENWOOD)
(PC700: sanwa)PC Link 7: sanwa
Ar 510
152050100150 Pa 0
0 1 1 5
Ar 3.10
3.9 Ar DC
1k
10 k, 15 k, 100 k,
200 k or 1 M
TMP RP
MFC
Ar
V1 V2 0~-1k V
PC
15
3.10 CVD DC Ar(50 Pa)
3.4
3.11 1 M 100 k 5 Pa
10-4 mA 10-1 mA-700 V
0.1 mA
0.2 mA 1 mA
1 mA-940 V 0.2 mA 1 mA
1 2
100 V
3.11 5 Pa
(a)1 M(b)100 k
3.12 1 M200 k10 k 20 Pa
10-3 mA 10-1 mA-320-300 V
10-4 10-3 10-2 10-1 1000
200
400
600
800
1000(a)1 M
1st2nd3rd4th5th
10-3 10-2 10-1 100 1010
200
400
600
800
1000
Current (mA)
(b)100 k
Vo
ltag
e (V
)
1st2nd3rd4th5th
16
0.15 mA 10 mA-480 V
1 M5 Pa
3.12 20 Pa
(a)1 M(b)200 k(c)10 k
3.13 150 Pa 10-2 mA 101 mA -300 V
-220 V 10 mA
100 mA-350 V 1
3.13 150 Pa
(a)1 M(b)200 k(c)10 k
10-3 10-2 10-1 1000
100
200
300
400
500(b)200 k
1st2nd3rd4th5th
10-3 10-2 10-1 100 1010
100
200
300
400
500
Current (mA)
(c)10 k
1st2nd3rd4th5th
10-4 10-3 10-2 10-1 1000
100
200
300
400
500
1st2nd3rd4th5th
(a)1 M
Volt
age
(V)
10-2 10-1 1000
100
200
300
400(b)200 k
1st2nd3rd4th5th
10-1 100 101 1020
100
200
300
400
Current (mA)
(c)10 k
1st2nd3rd4th5th
10-3 10-2 10-1 1000
100
200
300
400(a)1 M
Volt
age
(V)
1st2nd3rd4th5th
17
3.5
3.14 5
10-3 mA 102 mA
5 Pa 20 Pa 10-3 mA 10-1 mA
10-1 mA 50 Pa 150
Pa 10-2 mA 100 mA100 mA
V p d pd
3.15 pd > (pd)min p
V pd < (pd)
min p
V
pd < (pd)min
3.14
510152050100150 Pa 10 k15 k100 k200 k1 M
10-4 10-3 10-2 10-1 100 101 1020
100
200
300
400
500
600
700
800
900
1000
Current (mA)
Volt
age
(V)
50 Pa 10 k50 Pa 200 k50 Pa 1 M
20 Pa 10 k 20 Pa 200 k20 Pa 1 M
100 Pa 10 k100 Pa 200 k100 Pa 1 M
150 Pa 10 k150 Pa 200 k150 Pa 1 M
15 Pa 15 k
10 Pa 15 k10 Pa 100 k
5 Pa 100 k5 Pa 1 M
18
3.15
3.6
3.16 Ar 20 Pa 100
4 1
3.17 20 Pa
25
10 mA-500 V 400-780 V
3.16 100
pd
V
pdmin
Vmin
10-4 10-3 10-2 10-1 100 1010
200
400
600
800
10001st2nd3rd4th
20 Pa 100
Current (mA)
Vo
ltag
e (V
)
19
3.17
3.7
3.7.1
1 1
2
nm2
[15]
2 [16] 1
2
2
100
3.7.2
P V N
k Tg Ts
=
n
=
=
P Ts
Tg V N
10-4 10-3 10-2 10-1 100 1010
200
400
600
800
1000
Current (mA)
Vo
ltag
e (V
)
40030020010025
20
n
21
4 DC DLC
DC DLC
[17-19]DLC
CO DC CVD DLC
MOSFET
DLCRF CVD
DLC
4.1 CO DLC
4.1.1
CO 2.4
0.010.2 ppm
CH4
COCO
12.574. 2 vol%CO
4.1 [20]
4.1.2 DC
4.1 DC DC
DC MOSFET
DLC 10 mA MOSFET
28.0104
-191.5
[m3/kg](1atm, 21.1) 0.861
0.967=1, 1atm, 0
3.537cm3/100cm3 H2O (1atm, 0)
CO2H2
22
4.1 DC
4.1.3
4.2 CO DC 4
Sin < 0.02 cm
4.2 CO 100 sccm (LG-11S:
ANELVA)40 Pa 300 Pa 25 300
25 kHz50 %40 Pa
RF CVD CO DLC (80
nm/min) 530
300 Pa
10
532.08 nm HORIBA JOVIN IVON HR-800
23
4.2 DC
4.2 DC
4.3(a)40 Pa (b)300 Pa DC CO
40 Pa300 Pa40 Pa
300 Pa
Si
AC 100 VDMM
5 Vp-p
CO
CO
(sccm)
(Pa)
()
(kHz)
(%)
(min)
1 25
2 300
3 25
4 100
5 200
6 300
100
40 30
300
20 50
10
24
4.3 (a)40 Pa(b)300 Pa DC CO
CVD DC
4.4 RF CVD 4.3CO
MFC 100 sccm 40 Pa RF
100 W 300 nm 4.4 RF
CVD DLC
4.4 RF CVD
4.3 RF CVD DLC
(a) 40 Pa (b) 300 Pa
CO
RF (13.56 MHz)
Si RF
G
CO
(sccm)
(Pa)
RF
(W)
(V)
(min)
100 40 100 -900 3.6
25
4.4 RF CVD DLC
4.2
4.5 DC Si CO DLC
2 40 Pa 300 87 mm
4.6(a)(b)
DC 4.6(c)
RF CVD CO DLC
1300 cm-1 1600 cm-11360
cm-1 1590 cm-1 DLC 1350 cm-1
1580 cm-1 DG
DLC
4.5 DC Si CO DLC 40 Pa
300
C2H2 CO
H(atm%)(RBS/ERDA) 27 4
O(atm%)(RBS) 0 20
(@550 nm) 2.3 2.1
(@550 nm) 0.27 0.45
(GPa) 21.5 15.1
(cm) >109 0.2
26
4.6 DC (a)40 Pa(b)300 Pa RF(c)40 Pa
4.7 DLC 2
2
1380 cm-1 D1580 cm-1
G 4.8(a)G
(cm-1)(b)G(cm-1) D I(D) G
I(G)(c)I(D)/I(G) 40 Pa 300 Pa
300 Pa GI(D)/I(G)
300 Pa 40 Pa
6 DLC
RF
CVD DLC 1 DLC
RF GI(D)/I(G)
1000 1500 2000
(c) RF 40 Pa
25
300
200
300
1000 1500 2000 1000 1500 2000
(b) Pulse 300 Pa(a) Pulse 40 Pa
25
100
Raman shift (cm-1
)
Inte
nsi
ty (
arb
. u
nit
)
27
4.7 DLC
4.8 (a)G(cm-1)(b)G(cm-1)
(c)I(D)/I(G)
1000 1500 20000
100
200
300
Raman shift (cm-1
)
Inte
nsi
ty (
arb.
unit
)
D
G
40 Pa 25
1560
1590
1620
G p
osi
tio
n (
cm-1
)
100
150
200
FW
HM
of
G p
eak
(cm
-1)
0 100 200 300
2
4
I(D
)/I(
G)
(a)
(b)
(c)
Pulse 40 PaPulse 300 PaRF 40 Pa
Electrode temperature ()
28
5
CO CVD ta-C
CVD
CVD
DC Ar
5 Pa 150 Pa
1
2
2
CVDDC CO DLC
DLC
DLC
[1] Y. Konishi, et al., Nuclear Instrument and Methods in Physics Research Section B 118(1996) 312.
[2] Y. Yasuoka et al., Japanese Journal of Applied Physics 54, 01AD04 (2015).
[3] New Diamond Vol. 28 No. 3 (2012) p7.
[4] New Diamond Vol.28 No.3 (2012) p17.
[5] Shi Xu, L. K. Cheah, B. K. Tay, Thin Solid Films, 312, 1-2, (1998), 160.
[6] , , 2011
[7] Y. Liou, R. Weimer, D. Knight, and R. Messier, Appl. Phys. Lett., 56 (1990) 437.
[8] N. Ohtake, T. Saito, Y. Kondo, S. Hosono, Y. Nakamura, and Y. Imanishi, Jpn. J. Appl. Phys. 43
(2004) L1406.
[9] J. Robertson, Diamond Relat. Mater. 2, 984(1993).
[10] K. Yamamoto et al., Diamond Relat. Mater. 10, 895(2001).
[11] J. Robertson, Diamond Relat. Mater. 3, 361(1994).
[12] Y. P. Raizer, Gas Discharge Physics (Springer Verlag. 1991).
[13] 1900
[14] 69 33 1991
[15] E.V. Alonso, R.A. Baragiola, J. Ferrn and A. Oliva-Florio, Rad. Effects 45,119 (1979).
[16] S. Hiroki et al., JAERI-M 85-123 (1985).
29
[17] T. Michler et al., Diamond Relat. Mater. 7, 459 (1998).
[18] H. Mori and H. Tachikawa, Surf. Coatings Technol. 149, 224 (2002).
[19] 50, 401 (2008).
[20] (1989)
1. Y. Yasuoka , T. Harigai, J.-S. Oh, H. Furuta, A. Hatta, T. Suzuki, and H. Saitoh, Diamond-Like
Carbon Films from CO Source Gas by RF Plasma CVD Method, Jpn. J. Appl. Phys. (accepted, 2014)
2. T. Harigai, Y. Yasuoka, N. Nitta, H. Furuta, and A. Hatta, "X-ray Reflectivity Analysis on Initial Stage
of Diamond-Like Carbon Film Deposition on Si Substrate by RF Plasma CVD and on Removal of the
Sub-Surface Layer by Oxygen Plasma Etching", Diamond Relat. Mater. 38 (2013) 36.
1. CO
RF CVD DLC2014.03.19.
2.
DLC2014.07.07.
3. CO DLC
2014.09.19.
1. Y. Yasuoka, M. Kakuta, J.-S. Oh, H. Furuta, A Hatta, Non-thermal atmospheric-pressure helium
plasma jet etched DLC film in ambient air., ISSP 2015(2015.07.09)
30